Catalyst system and its use in a polymerization process

ABSTRACT

Disclosed are polymerization catalyst activator compositions which include a carbonium cation and an aluminum containing anion. These activator compositions are prepared by combining a carbonium or trityl source and with an aluminum containing complex, preferably a perfluorophenylaluminum compound. Also disclosed are polymerization catalyst systems including the activator composition of the invention, and processes for polymerizing olefins utilizing same.

RELATED APPLICATION DATA

[0001] The present application is a divisional of U.S. patentapplication Ser. No. 09/649,746, filed Aug. 28, 2000, now issued as U.S.Pat. No. ______.

FIELD OF THE INVENTION

[0002] The present invention relates to catalyst activator compositions,to methods of making these activator compositions, to polymerizationcatalyst systems containing these activator compositions, and toolefin(s) polymerization processes utilizing same. More specifically,the present application relates to the preparation and use of carboniumsalt complexes containing at least one anionic aluminum, to catalystsystems containing these complexes, and to polymerization processesutilizing same.

BACKGROUND OF THE INVENTION

[0003] Polymerization catalyst compounds, including bulky ligandmetallocene catalyst compounds, are typically combined with an activator(or co-catalyst) to yield compositions having a vacant coordination sitethat will coordinate, insert, and polymerize olefins. Known activatorsincluded alumoxane, modified alumoxanes, aluminum alkyls, and ionizingactivators. Examples of neutral ionizing activators include Group 13based Lewis acids having three fluorinated aryl substituents, andexamples of ionic ionizing activators include ammonium cations or tritylcations (triphenylcarbenium) combined with noncoordinating/weaklycoordinating borate or aluminate anions.

[0004] Alumoxane activators are generally oligomeric compoundscontaining —Al(R)—O— subunits, where R is an alkyl group. Examples ofalumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alumoxanes may be producedby the hydrolysis of the respective trialkylaluminum compound. MMAO maybe produced by the hydrolysis of trimethylaluminum and a highertrialkylaluminum such as triisobutylaluminum. MMAO's are generally moresoluble in aliphatic solvents and more stable during storage. A varietyof methods for preparing alumoxanes and modified alumoxanes aredescribed in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199,5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815,5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793,5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177,5,854,166, 5,856,256 and 5,939,346 and European publications EP-A-0 561476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCTpublication WO 94/10180. Known alumoxane activators are also disclosedin U.S. Patent No. 5,041,584. Another known activator, modified methylalumoxane in heptane (MMAO3A) is commercially available from AkzoChemicals, Inc., Houston, Tex. Alumoxanes, however, must generally bepresent in a large excess over the catalyst compound to be effectiveactivators, which significantly increases the costs of such catalystsystems.

[0005] Aluminum alkyl compounds, including trialkylaluminums and alkylaluminum chlorides, are also known to be useful as activators. Examplesof these compounds include trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike.

[0006] Neutral ionizing activators include Group 13 based Lewis acids,having three fluorinated aryl substituents, are capable of activatingolefin polymerization catalysts. Specific examples of these activatorsinclude trisperfluorophenyl boron and trisperfluoronapthyl boron.Trisperfluorophenylborane, is demonstrated in EP-A1-0 425 697 A1 andEP-B1-0 520 732 to be capable of abstracting a ligand forcyclopentadienyl derivatives of transition metals while providing astabilizing, compatible noncoordinating anion. See also, Marks, et al,J. Am. Chem. Soc. 1991, 113, 3623-3625. The noncoordinating anions aredescribed to function as electronic stabilizing cocatalysts, orcounterions, for cationic metallocene complexes which are active forolefin polymerization. The term noncoordinating anion as used hereinapplies to noncoordinating anions and coordinating anions that are atmost weakly coordinated to the cationic complex so as to be labile toreplacement by olefinically or acetylenically unsaturated monomers atthe insertion site. The synthesis of Group 13-based compounds derivedfrom trisperfluorophenylborane are described in EP 0 694 548 A1. TheseGroup 13-based compounds are said to be represented by the formulaM(C₆F₅)₃ and are prepared by reacting the trisperfluorophenylborane withdialkyl or trialkyl Group 13-based compounds at a molar ratio of about1:1 so as to avoid mixed products, those including the type representedby the formula M(C₆F₅)_(n)R_(3−n), where n=1 or 2. Utility for thetris-aryl aluminum compounds in Ziegler-Natta olefin polymerization issuggested.

[0007] Ionizing ionic activators, for example, include ammonium cations,such as N,N-dimethylanilinium, or trityl cations (triphenylcarbenium ortrityl⁺) combined with noncoordinating/weakly coordinating borate oraluminate anions, such as, for example tetra(perfluorophenyl)borate.Such compounds and the like are described in European publicationsEP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401,5,066,741, 5,206,197, 5,241,025, 5,384,299, 5,447,895 and 5,502,124 andU.S. patent application Ser. No. 08/285,380, filed Aug. 3, 1994, all ofwhich are fully incorporated herein by reference.

[0008] Perfluorophenyl-aluminum complexes, however, have been implicatedas possible deactivation sources in olefin polymerizations which utilizeTrityl⁺ B(C₆F₅)₄ ⁻/alkylaluminum combinations to activate the catalysts.See, Bochmann, M.; Sarsfield, M. J.; Organometallics 1998, 17, 5908.Perfluorophenylaluminum (toluene), for example, has been characterizedvia X-ray crystallography. See, Hair, G. S., Cowley, A. H., Jones, R.A., McBumett, B. G.; Voigt, A., J. Am. Chem. Soc., 1999, 121, 4922.Arene coordination to the aluminum complex demonstrates the Lewisacidity of the aluminum center. Bochmann and Sarsfield have shown thatCp₂ZrMe₂ reacts with Al(C₆F₅)₃0.5(toluene) with transfer of the C₆F₅ ⁻moiety forming metallocene pentafluorophenyl complexes. These complexes,however, were reported having very low activity compared to thecorresponding metallocene dimethyl complexes when activated withB(C₆F₅)₃ or Trityl⁺ B(C₆F₅)₄ ⁻.

[0009] The supporting of ionic activators, however, typically results ina significant loss of activity. Supported non-coordinating anionsderived from trisperfluorophenyl boron are described in U.S. Pat. No.5,427,991. Trisperfluorophenyl boron is shown to be capable of reactingwith coupling groups bound to silica through hydroxyl groups to formsupport bound anionic activators capable of activating transition metalcatalyst compounds by protonation. U.S. Pat. Nos. 5,643,847 and5,972,823 discuss the reaction of Group 13 Lewis acid compounds withmetal oxides such as silica and illustrate the reaction oftrisperfluorophenyl boron with silanol groups (the hydroxyl groups ofsilicon) resulting in bound anions capable of protonating transitionmetal organometallic catalyst compounds to form catalytically activecations counter-balanced by the bound anions.

[0010] Immobilized Group IIIA Lewis acid catalysts suitable forcarbocationic polymerizations are described in U.S. Pat. No. 5,288,677.These Group IIIA Lewis acids are said to have the general formulaR_(n)MX_(3−n) where M is a Group IIIA metal, R is a monovalenthydrocarbon radical consisting of C, to C₁₂ alkyl, aryl, alkylaryl,arylalkyl and cycloalkyl radicals, n=0 to 3, and X is halogen. ListedLewis acids include aluminum trichloride, trialkyl aluminums, andalkylaluminum halides. Immobilization is accomplished by reacting theseLewis acids with hydroxyl, halide, amine, alkoxy, secondary alkyl amine,and other groups, where the groups are structurally incorporated in apolymeric chain. James C. W. Chien, Jour. Poly. Sci.: Pt A: Poly. Chem,Vol. 29, 1603-1607 (1991), describes the olefin polymerization utilityof methylalumoxane (MAO) reacted with SiO₂ and zirconocenes anddescribes a covalent bonding of the aluminum atom to the silica throughan oxygen atom in the surface hydroxyl groups of the silica.

[0011] Additional compounds useful as activators also include thosedescribed in PCT publications WO 98/07515, which discloses tris (2, 2′,2″-nonafluorobiphenyl) fluoroaluminate, WO 98/09996, which describesactivating bulky ligand metallocene catalyst compounds withperchlorates, periodates and iodates including their hydrates, WO98/30602 and WO 98/30603, which describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate).4THF as an activator for a bulkyligand metallocene catalyst compound, WO 99/18135 which describes theuse of organo-boron-aluminum acitivators, and in EP-B 1-0 781 299 whichdescribes using a silylium salt in combination with a non-coordinatingcompatible anion, all of which are herein fully incorporated byreference. Further activators or methods for activating a bulky ligandmetallocene catalyst compound are described in for example, U.S. Pat.Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO 99/42467(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are also fully incorporated herein byreference.

[0012] U.S. Pat. No. 5,895,771 discloses a catalyst compositioncomprising a neutral metallocene and an anionic aluminum containingcomplex which is a fluorinated alkoxy and/or arylalkoxy aluminate wherethe fluorinated alkoxy aluminate can be of the formula A⁺(Al(OR)₄)⁻.

[0013] Harney, D. W et al., Aust. J. Chem. (1974) 27, 1639, discuss thereaction of triphenylmethanol and trimethylaluminum. Water is reportedto catalyze the formation of 1,1,1-triphenylethane from the reaction oftrimethylaluminum and [Me₂AlOC(C₆H₅)₃]₂.

[0014] WO 99/15534 reports the reaction of methylalumoxane andtris-pentafluorophenylaluminum.

[0015] WO 99/06414 reports compounds of the formula [R2B—X—AlR,R]_(x).

[0016] While these catalyst activator compounds have been described inthe art, there is still a need for improved catalyst activators, foractivators suitably for anchoring on supports, and for catalyst systemsutilizing such activators.

SUMMARY OF THE INVENTION

[0017] This invention provides new polymerization catalyst activatorcompositions including a carbonium cation and an aluminum containinganion. These activator compositions are prepared by combining acarbonium or trityl source and with an aluminum containing complex,preferably a perfluorophenylaluminum compound. The invention alsoprovides for methods of making the activator compositions of theinvention, a polymerization catalyst system which includes the activatorcomposition of the invention, and a process for polymerizing olefinsutilizing same.

SUMMARY OF THE FIGURES

[0018]FIG. 1 is an illustration of the complex having the formula:(C₆H₅)₃C⁺[HO(Al(C₆F₅)₃)₂]⁻ prepared in Example 1.

[0019]FIG. 2 is an ¹⁹F NMR of (C₆H₅)₃C⁺[HO(Al(C₆F₅)₃)₂]³¹ prepared inExample 1.

DETAILED DESCRIPTION OF THE INVENTION

[0020] New carbonium salt activator compositions, having an anioncontaining at least one aluminum atom have been discovered. Preferably,the activator composition of the invention includes a carbonium saltcontaining an aluminum anion such that in the resulting complex containsat least one anionic aluminum. The activator composition of theinvention may be prepared by combining a carbonium or trityl source andwith an aluminum containing complex. The resulting trityl-alumoxanecomplexes have been found to activate polymerization catalyst compounds.

[0021] The activators of the invention are the compositions produced bythe combination of perfluorophenylaluminum compounds with a tritylsource. In one embodiment, the perfluorophenylaluminum compound may berepresented by formula (I):

Al(C₆F₅)_(m)R_(n)   (I)

[0022] where m+n=3 and each R is independently a monoanionic ligand,hydrogen, an hydroxyl group, an alkyl group, or R may be represented bythe formula ArHal, where ArHal a halogenated C₆ aromatic or highercarbon number polycyclic aromatic hydrocarbon or aromatic ring assemblyin which two or more rings (or fused ring systems) are joined directlyto one another or together. Alternatively, R may be represented byformula [M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is aninteger from 2 to 6; n−k=d; M is an element selected from Group 13 ofthe Periodic Table of the Elements and Q is independently a hydride,bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having upto 20 carbon atoms.

[0023] An alkyl group may be a linear or branched alkyl radical, alkenylradical, alkynyl radical, cycloalkyl radical or aryl radicals, an acylradical, aroyl radical, alkoxy radical, aryloxy radical, alkylthioradical, dialkylamino radical, alkoxycarbonyl radical, aryloxycarbonylradical, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radical,acyloxy radicals, acylamino radical, aroylamino radical, straight,branched or cyclic alkylene radical, or combination thereof. Anarylalkyl group is defined to be a substituted aryl group.

[0024] Suitable non-limiting examples of R ligands include: substitutedor unsubstituted C₁ to C₃₀ hydrocarbyl aliphatic or aromatic groups,substituted meaning that at least one hydrogen on a carbon atom isreplaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl orhalocarbyl substituted organometalloid, dialkylamido, alkoxy, siloxy,aryloxy, alkysulfido, arylsulfido, alkylphosphido, alkylphosphido orother anionic substituent; fluoride; bulky alkoxides, where bulky refersto C₄ and higher number hydrocarbyl groups, e.g., up to about C₂₀, suchas tert-butoxide and 2,6-dimethyl-phenoxide, and2,6-di(tert-butyl)phenoxide; —SR; —NR₂, and —PR₂, where each R isindependently a substituted or unsubstituted hydrocarbyl as definedabove; and, C₁ to C₃₀ hydrocarbyl substituted organometalloid, such astrimethylsilyl.

[0025] Examples of ArHal include the phenyl, napthyl and anthracenylradicals of U.S. Pat. No. 5,198,401 and the biphenyl radicals of WO97/29845 when halogenated, both incorporated herein by reference. Theuse of the terms halogenated or halogenation, for purposes of thispatent specification and appended claims, mean that at least one thirdof hydrogen atoms on carbon atoms of the aryl-substituted aromaticligands are replaced by halogen atoms. More preferably, the aromaticligands are perhalogenated, where the preferred halogen is fluorine.

[0026] In one embodiment, the trityl source is represented by theformula II:

(C₆H₅)₃COL   (II)

[0027] where L is a metal moiety, a metalloid moiety, or L is the sameas R as defined above.

[0028] A metal moiety is a metal atom containing group. Examples ofmetal atom(s) are those selected from Groups 3 through 15 and thelanthanide or actinide series of the Periodic Table of Elements.Preferred metals containing groups include Al, K, Mg, Na, Si, Ti and Zr.Non-limiting examples of metal atom containing groups include AlR₂,TiR₃, Ti(Bz)₃ or ZrR₃ where R is as defined above and where Bz isbenzyl.

[0029] A metalloid moiety is an metalloid atom containing group.Examples of metalloid atoms include B, Al, Si, Ge, As, Sb, Te, Po andAs.

[0030] In one embodiment, L may be represented by formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2 to 6; n−k=d; M is an element selected from Group 13 of thePeriodic Table of the Elements and Q is independently a hydride, bridgedor unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, andhalosubstituted-hydrocarbyl radicals, Q having up to 20 carbon atoms.

[0031] In one embodiment, the complex resulting from combining theperfluorophenyl aluminum compound of formula I and the trityl source offormula II may be represented generally by formula III:

[Al(C₆F₅)_(m)R_(n)]_(x)[(C₆H₅)₃COL]_(y)   (III)

[0032] where, in formula II, x and y may or may not be integers andrepresent the ratio in which the perfluorophenylaluminum complex(formula I) and the trityl source (formula II) were combined, and whereR, L, m and n are as defined above.

[0033] In another embodiment, the perfluorophenylaluminum complex may berepresented generally by formula IV:

(AlO)_(x)(Al)_(y)(C₆F₅)_(z)(R)_(d)   (IV)

[0034] where, in formula IV, x cannot be 0; x+y≧2; if y=0 then x≧2; Rmay be OH, R or OR, where R is as defined above; R may bridge to the Al;z+d is ≦1+3(x+y) where x, y, z and d represent the ratio in which thecomponents combine and may or may not be integers.

[0035] While not being limited by theory, it is believed that theperfluorophenylaluminum complexes, represented by formulae I and IV,react with the compounds of formula II inserting into the C—O bond andforming an aluminum oxygen bond with the reaction driven by theoxophilicity of the perfluorophenylaluminum complex. In the absence ofan anionic moiety available for reaction with the resulting (C₆H₅)₃C⁺cation, trityl salts are obtained.

[0036] In another embodiment, other activators or methods of activationare contemplated for use with the activator(s) described above. Forexample, the activators of the invention may be used in combination withother activators including alumoxane, modified alumoxane, tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronapthyl boron metalloid precursor,polyhalogenated heteroborane anions, trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, tris (2, 2′, 2″-nonafluorobiphenyl)fluoroaluminate,perchlorates, periodates, iodates and hydrates,(2,2′-bisphenyl-ditrimethylsilicate).4THF and organo-boron-aluminumcompound, silylium salts anddioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)-benzimidazolideor combinations thereof.

[0037] Catalyst Compounds

[0038] The activator compositions of the invention may be utilized inconjunction with any suitable polymerization catalyst compound orcompounds to polymerize olefins. In a preferred embodiment, the catalystcompositions contain alkyl leaving groups. Examples of suitable catalystcompounds include bulky ligand metallocene catalyst compositions, metalcontaining Group 15 polymerization catalyst compositions and phenoxidetransition metal catalyst compositions.

[0039] Bulky Ligand Metallocene Catalyst Compositions

[0040] The activator compositions of the present invention may be usedto activate bulky ligand metallocene catalyst compositions. Generally,these catalyst compounds include half and full sandwich compounds havingone or more bulky ligands bonded to at least one metal atom. Typicalbulky ligand metallocene compounds are described as containing one ormore bulky ligand(s) and one or more leaving group(s) bonded to at leastone metal atom.

[0041] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.The ring(s) or ring system(s) of these bulky ligands are typicallycomposed of atoms selected from Groups 13 to 16 atoms of the PeriodicTable of Elements. Preferably the atoms are selected from the groupconsisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous,germanium, boron and aluminum or a combination thereof. Most preferablythe ring(s) or ring system(s) are composed of carbon atoms such as butnot limited to those cyclopentadienyl ligands or cyclopentadienyl-typeligand structures or other similar functioning ligand structure such asa pentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atomis preferably selected from Groups 3 through 15 and the lanthanide oractinide series of the Periodic Table of Elements. Preferably the metalis a transition metal from Groups 4 through 12, more preferably Groups4, 5 and 6, and most preferably the transition metal is from Group 4.

[0042] In one embodiment, the bulky ligand metallocene catalystcompounds, which may be utilized with the activator composition of theinvention, may be represented by the formula:

L^(A)L^(B)MQ_(n)   (V)

[0043] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthanide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is zirconium, hafnium ortitanium. The bulky ligands, L^(A) and L^(B), are open, acyclic or fusedring(s) or ring system(s) and are any ancillary ligand system, includingunsubstituted or substituted, cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Non-limiting examples of bulkyligands include cyclopentadienyl ligands, cyclopentaphenanthreneylligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding . In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u.. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (V) only one of either L^(A) or L^(B) is present.

[0044] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0045] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. For the purposes of this patent specification andappended claims the term “leaving group” is any ligand that can beabstracted from a bulky ligand metallocene catalyst compound to form abulky ligand metallocene catalyst cation capable of polymerizing one ormore olefin(s). In one embodiment, Q is a monoanionic labile ligandhaving a sigma-bond to M. Depending on the oxidation state of the metal,the value for n is 0, 1 or 2 such that formula (I) above represents aneutral bulky ligand metallocene catalyst compound.

[0046] Non-limiting examples of Q ligands include weak bases such asamines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicalshaving from 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

[0047] In another embodiment, the activator composition of the inventionis utilized with the bulky ligand metallocene catalyst compounds offormula (VI) where L^(A) and L^(B) are bridged to each other by at leastone bridging group, A, as represented in the following formula:

L^(A)AL^(B)MQ_(n)   (VI)

[0048] These bridged compounds represented by formula (VI) are known asbridged, bulky ligand metallocene catalyst compounds. L^(A), L^(B), M, Qand n are as defined above. Non-limiting examples of bridging group Ainclude bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene catalyst compounds of formula (VI) have two or more bridginggroups A (EP 664 301 B1).

[0049] In another embodiment, the activator composition of the inventionmay be utilized with bulky ligand metallocene catalyst compounds wherethe R substituents on the bulky ligands L^(A) and L^(B) of formulas (V)and (VI) are substituted with the same or different number ofsubstituents on each of the bulky ligands. In another embodiment, thebulky ligands L^(A) and L^(B) of formulas (V) and (VI) are differentfrom each other.

[0050] In another embodiment, the activator composition of the inventionmay be utilized with other bulky ligand metallocene catalyst compoundssuch as those described in U.S. Pat. Nos. 5,064,802, 5,145,819,5,149,819, 5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106,5,329,031, 5,304,614, 5,677,401, 5,723,398, 5,753,578, 5,854,363,5,856,547 5,858,903, 5,859,158, 5,900,517 and 5,939,503 and PCTpublications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 andEuropean publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380,EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0 748 821 andEP-B1-0 757 996, all of which are fully incorporated herein byreference.

[0051] In another embodiment, the activator composition of the inventionmay be utilized with bulky ligand metallocene catalysts which includebridged heteroatom, mono-bulky ligand metallocene compounds. These typesof catalysts and catalyst systems are described in, for example, PCTpublication WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506,W096/00244, WO 97/15602 and WO 99/20637 and U.S. Pat. Nos. 5,057,475,5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and Europeanpublication EP-A-0 420 436, all of which are herein fully incorporatedby reference.

[0052] In this embodiment, the activator compositions of the inventionare utilized with a bulky ligand metallocene catalyst compoundrepresented by formula (VII):

L^(C)AJMQ_(n)   (VII)

[0053] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthanides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillaryligand; and A is a bridging group; Q is a univalent anionic ligand; andn is the integer 0,1 or 2. In formula (VII) above, L^(C), A and J form afused ring system. In an embodiment, L^(C) of formula (VII) is asdefined above for L^(A), A, M and Q of formula (VII) are as definedabove in formula (V).

[0054] In formula (VII) J is a heteroatom containing ligand in which Jis an element with a coordination number of three from Group 15 or anelement with a coordination number of two from Group 16 of the PeriodicTable of Elements. Preferably J contains a nitrogen, phosphorus, oxygenor sulfur atom with nitrogen being most preferred.

[0055] In another embodiment, the activator composition of the inventionis utilized with a bulky ligand type metallocene catalyst compound whichis a complex of a metal, preferably a transition metal, a bulky ligand,preferably a substituted or unsubstituted pi-bonded ligand, and one ormore heteroallyl moieties, such as those described in U.S. Pat. Nos.5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which are hereinfully incorporated by reference.

[0056] In another embodiment the activator composition of the inventionis utilized with a ligand metallocene catalyst compound which may berepresented by formula VIII:

L^(D)MQ₂(YZ)X_(n)   (VIII)

[0057] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; L^(D) is a bulky ligand that is bonded to M; each Q isindependently bonded to M and Q₂(YZ) forms a unicharged polydentateligand; A or Q is a univalent anionic ligand also bonded to M; X is aunivalent anionic group when n is 2 or X is a divalent anionic groupwhen n is 1; n is 1 or 2.

[0058] In formula (VIII), L and M are as defined above for formula (V).Q is as defined above for formula (V), preferably Q is selected from thegroup consisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0059] In another embodiment, the activator composition of the inventionis utilized with a the bulky ligand metallocene catalyst compounds,which include heterocyclic ligand complexes where the bulky ligands, thering(s) or ring system(s), include one or more heteroatoms or acombination thereof. Non-limiting examples of heteroatoms include aGroup 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen,aluminum, silicon, phosphorous and tin. Examples of these bulky ligandmetallocene catalyst compounds are described in WO 96/33202, WO96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Pat.No. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417,and 5,856,258 all of which are herein incorporated by reference.

[0060] In another embodiment, the activator composition of the inventionmay be utilized with bulky ligand metallocene catalyst compounds, whichinclude complexes known as transition metal catalysts based on bidentateligands containing pyridine or quinoline moieties, such as thosedescribed in U.S. application Ser. No. 09/103,620 filed Jun. 23, 1998,which is herein incorporated by reference. In another embodiment, thebulky ligand metallocene catalyst compounds are those described in PCTpublications WO 99/01481 and WO 98/42664, which are fully incorporatedherein by reference.

[0061] In another embodiment, the activator composition of the inventionmay be utilized with a bulky ligand metallocene catalyst compounds whichmay be represented by formula IX:

((Z)XA_(t)(YJ))_(q)MQ_(n)   (IX)

[0062] where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X,Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

[0063] It is also within the scope of this invention, in one embodiment,that the bulky ligand metallocene catalyst compounds, which may beutilized with the activator composition of the invention includecomplexes of Ni²⁺ and Pd²⁺ described in the articles Johnson, et al.,“New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethyleneand a-Olefins”, J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, etal., “Copolymerization of Ethylene and Propylene with FunctionalizedVinyl Monomers by Palladium(II) Catalysts”, J. Am. Chem. Soc., 1996,118, 267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S.Pat. Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fullyincorporated by reference. These complexes can be either dialkyl etheradducts, or alkylated reaction products of the described dihalidecomplexes that can be activated to a cationic state by the activators ofthis invention described below.

[0064] Also included as bulky ligand metallocene catalyst are thosediimine based ligands of Group 8 to 10 metal compounds disclosed in PCTpublications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem.Comm., pp. 849-850 (1998), all of which are herein incorporated byreference.

[0065] Other bulky ligand metallocene catalysts, which may be utilizedwith the activator composition of the invention, are those Group 5 and 6metal imido complexes described in EP-A2-0 816 384 and U.S. Pat. No.5,851,945, which is incorporated herein by reference. In addition,bridged bis(amido) catalyst compounds are described in WO 96/27439,which is herein incorporated by reference. Other bulky ligandmetallocene catalysts are described as bis(hydroxy aromatic nitrogenligands) in U.S. Pat. No. 5,852,146, which is incorporated herein byreference. Other metallocene catalysts containing one or more Group 15atoms include those described in WO 98/46651, which is hereinincorporated herein by reference. Still another metallocene bulky ligandmetallocene catalysts include those multinuclear bulky ligandmetallocene catalysts as described in WO 99/20665, which is incorporatedherein by reference.

[0066] It is also contemplated that in one embodiment, the bulky ligandmetallocene catalysts of the invention described above include theirstructural or optical or enantiomeric isomers (meso and racemic isomers,for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

[0067] Group 15 Containing Polymerization Catalyst

[0068] The activator compositions of the invention may also be utilizedwith metal containing Group 15 polymerization catalyst compounds.Generally, these catalysts includes a Group 3 to 14 metal atom,preferably a Group 3 to 7, more preferably a Group 4 to 6, and even morepreferably a Group 4 metal atom, bound to at least one leaving group andalso bound to at least two Group 15 atoms, at least one of which is alsobound to a Group 15 or 16 atom through another group.

[0069] Preferably, at least one of the Group 15 atoms is also bound to aGroup 15 or 16 atom through another group which may be a C₁ to C₂₀hydrocarbon group, a heteroatom containing group, silicon, germanium,tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also bebound to nothing or a hydrogen, a Group 14 atom containing group, ahalogen, or a heteroatom containing group, and wherein each of the twoGroup 15 atoms are also bound to a cyclic group and may optionally bebound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or aheteroatom containing group.

[0070] In another embodiment of the invention the composition containingalternating atoms of Group 14 and Group 16 may be used to createsolutions or emulsions including one or more bulky ligandmetallocene-type catalyst compounds, and one or more conventional-typecatalyst compounds or catalyst systems. Non-limiting examples of mixedcatalysts and catalyst systems are described in U.S. Pat. Nos.4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867,5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCTPublication WO 96/23010 published Aug. 1, 1996, all of which are hereinfully incorporated by reference.

[0071] Metal containing Group 15 catalyst compounds may be representedby the formulae:

[0072] wherein M is a Group 3 to 12 transition metal or a Group 13 or 14main group metal, preferably a Group 4, 5, or 6 metal, and morepreferably a Group 4 metal, and most preferably zirconium, titanium orhafnium,

[0073] each X is independently a leaving group, preferably, an anionicleaving group, and more preferably hydrogen, a hydrocarbyl group, aheteroatom or a halogen, and most preferably an alkyl.

[0074] y is 0 or 1 (when y is 0 group L′ is absent),

[0075] n is the oxidation state of M, preferably +3, +4, or +5, and morepreferably +4,

[0076] m is the formal charge of the YZL or the YZL′ ligand, preferably0, −1, −2 or −3, and more preferably −2,

[0077] L is a Group 15 or 16 element, preferably nitrogen,

[0078] L′ is a Group 15 or 16 element or Group 14 containing group,preferably carbon, silicon or germanium,

[0079] Y is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0080] Z is a Group 15 element, preferably nitrogen or phosphorus, andmore preferably nitrogen,

[0081] R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, aheteroatom containing group having up to twenty carbon atoms, silicon,germanium, tin, lead, or phosphorus, preferably a C₂ to C₂₀ alkyl, arylor aralkyl group, more preferably a linear, branched or cyclic C₂ to C₂₀alkyl group, most preferably a C₂ to C₆ hydrocarbon group.

[0082] R³ is absent or a hydrocarbon group, hydrogen, a halogen, aheteroatom containing group, preferably a linear, cyclic or branchedalkyl group having 1 to 20 carbon atoms, more preferably R³ is absent,hydrogen or an alkyl group, and most preferably hydrogen

[0083] R⁴ and R⁵ are independently an alkyl group, an aryl group,substituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, a cyclic aralkyl group, a substituted cyclic aralkyl group ormultiple ring system, preferably having up to 20 carbon atoms, morepreferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkylgroup, or a heteroatom containing group, for example PR₃, where R is analkyl group,

[0084] R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵may be interconnected to each other,

[0085] R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent, and

[0086] R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, a heteroatom containing group.

[0087] By “formal charge of the YZL or YZL′ ligand”, it is meant thecharge of the entire ligand absent the metal and the leaving groups X.

[0088] By “R¹ and R² may also be interconnected” it is meant that R¹ andR² may be directly bound to each other or may be bound to each otherthrough other groups. By “R⁴ and R⁵ may also be interconnected” it ismeant that R⁴ and R⁵ may be directly bound to each other or may be boundto each other through other groups.

[0089] Phenoxide Transition Metal Catalyst Compositions

[0090] The activator compositions of the invention may also be used withphenoxide transtion metal catalyst compounds. Generally, these complexesare heteroatom substituted phenoxide ligated Group 3 to 10 transitionmetal or lanthanide metal compounds wherein the metal is bound to theoxygen of the phenoxide group.

[0091] Phenoxide transition metal catalyst compounds may be representedby formula XII or XIII below:

[0092] wherein R¹ is hydrogen or a C₄ to C,₁₀₀ group, preferably atertiary alkyl group, preferably a C₄ to C₂₀ alkyl group, preferably aC₄ to C₂₀ tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ groupand may or may not also be bound to M;

[0093] at least one of R² to R⁵ is a heteroatom containing group, therest of R² to R⁵ are independently hydrogen or a C₁ to C₁₀₀ group,preferably a C₄ to C₂₀ alkyl group, preferred examples of which includebutyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, isohexyl, octyl,isooctyl, decyl, nonyl, dodecyl, and any of R² to R⁵ also may or may notbe bound to M;

[0094] Each R¹ to R⁵ group may be independently substituted orunsubstituted with other atoms, including heteroatoms or heteroatomcontaining group(s);

[0095] O is oxygen;

[0096] M is a Group 3 to Group 10 transition metal or lanthanide metal,preferably a Group 4 metal, preferably M is Ti, Zr or Hf;

[0097] n is the valence state of the metal M, preferably 2, 3, 4, or 5;and

[0098] Q is, and each Q may be independently be, an alkyl, halogen,benzyl, amide, carboxylate, carbamate, thiolate, hydride or alkoxidegroup, or a bond to an R group containing a heteroatom which may be anyof R¹ to R⁵.

[0099] A heteroatom containing group may be any heteroatom or aheteroatom bound to carbon, silicon or another heteroatom. Preferredheteroatoms include boron, aluminum, silicon, nitrogen, phosphorus,arsenic, tin, lead, antimony, oxygen, selenium, tellurium. Particularlypreferred heteroatoms include nitrogen, oxygen, phosphorus, and sulfur.Even more particularly preferred heteroatoms include nitrogen andoxygen. The heteroatom itself may be directly bound to the phenoxidering or it may be bound to another atom or atoms that are bound to thephenoxide ring. The heteroatom containing group may contain one or moreof the same or different heteroatoms. Preferred heteroatom containinggroups include imines, amines, oxides, phosphines, ethers, ketones,oxoazolines heterocyclics, oxazolines, thioethers, and the like.Particularly preferred heteroatom containing groups include imines. Anytwo adjacent R groups may form a ring structure, preferably a 5 or 6membered ring. Likewise the R groups may form multi-ring structures. Inone embodiment any two or more R groups do not form a 5 membered ring.

[0100] In a preferred embodiment the heteroatom substituted phenoxidetransition metal compound is an iminophenoxide Group 4 transition metalcompound, and more preferably an iminophenoxidezirconium compound.

[0101] In another embodiment, it is further contemplated that the abovecatalysts or catalyst systems may be used in combination with theactivator(s) of the present invention.

[0102] Supports, Carriers and General Supporting Techniques

[0103] The activator complexes of the invention and/or thepolymerization catalyst compound may be combined with one or moresupport materials or carriers, using one of the support methods known inthe art or as described below. For example, in a one embodiment theactivator composition is in a supported form, for example deposited on,contacted with, vaporized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, a support or carrier. In anotherembodiment, the activator and a catalyst compound may be deposited on,contacted with, vaporized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, a support or carrier.

[0104] The terms “support” or “carrier”, for purposes of this patentspecification, are used interchangeably and are any support material,preferably a porous support material, including inorganic or organicsupport materials. Non-limiting examples of inorganic support materialsinclude inorganic oxides and inorganic chlorides. Other carriers includeresinous support materials such as polystyrene, functionalized orcrosslinked organic supports, such as polystyrene, divinyl benzene,polyolefins, or polymeric compounds, zeolites, talc, clays, or any otherorganic or inorganic support material and the like, or mixtures thereof.

[0105] The preferred carriers are inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, alumina, silica-alumina, magnesium chloride, and mixturesthereof. Other useful supports include magnesia, titania, zirconia,montmorillonite (EP-B1 0 511 665), phyllosilicate, and the like. Also,combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania and the like. Additionalsupport materials may include those porous acrylic polymers described inEP 0 767 184 B1, which is incorporated herein by reference.

[0106] It is preferred that the carrier, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the carrier of the invention typically has pore size in therange of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å.

[0107] Examples of supporting bulky ligand metallocene-type catalystsystems, which may be used to support the activator and/or catalystsystems of the invention are described in U.S. Pat. Nos. 4,701,432,4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892,5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766,5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015,5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402,5,731,261, 5,759,940, 5,767,032, 5,770,664, 5,846,895 and 5,939,348 andU.S. application Ser. Nos. 271,598 filed Jul. 7, 1994 and 788,736 filedJan. 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO 96/06187and WO 97/02297, and EP-B1-0 685 494 all of which are herein fullyincorporated by reference.

[0108] There are various other methods in the art for supporting thepolymerization catalyst systems of the invention. For example, the bulkyligand metallocene-type catalyst compound of the invention may contain apolymer bound ligand as described in U.S. Pat. Nos. 5,473,202 and5,770,755, which is herein fully incorporated by reference; the bulkyligand metallocene-type catalyst system of the invention may be spraydried as described in U.S. Pat. No. 5,648,310, which is herein fullyincorporated by reference; the support used with the bulky ligandmetallocene-type catalyst system of the invention may be functionalizedas described in European publication EP-A-0 802 203, which is hereinfully incorporated by reference, or at least one substituent or leavinggroup may be selected as described in U.S. Pat. No. 5,688,880, which isherein fully incorporated by reference.

[0109] In another embodiment, an antistatic agent or surface modifier,that is used in the preparation of the supported catalyst system asdescribed in PCT publication WO 96/11960, which is herein fullyincorporated by reference, may be used with catalyst systems includingthe activator compounds of the invention,. The catalyst systems of theinvention may also be prepared in the presence of an olefin, for examplehexene-1.

[0110] In another embodiment, activator and/or catalyst system of theinvention may be combined with a carboxylic acid salt of a metal ester,for example aluminum carboxylates such as aluminum mono, di- andtri-stearates, aluminum octoates, oleates and cyclohexylbutyrates, asdescribed in U.S. application Ser. No. 09/113,216, filed Jul. 10, 1998.

[0111] In another embodiment there is a method for producing a supportedbulky ligand metallocene-type catalyst system, which maybe used tosupport the activator of the invention which is described below, and isdescribed in U.S. application Ser. Nos. 265,533, filed Jun. 24, 1994 and265,532, filed Jun. 24, 1994 and PCT publications WO 96/00245 and WO96/00243 both published Jan. 4, 1996, all of which are herein fullyincorporated by reference. In this method, the catalyst compound isslurried in a liquid to form a catalyst solution or emulsion. A separatesolution is formed containing the activator. The liquid may be anycompatible solvent or other liquid capable of forming a solution or thelike with the catalyst compounds and/or activator. In the most preferredembodiment the liquid is a cyclic aliphatic or aromatic hydrocarbon,most preferably toluene. The catalyst compound and activator solutionsare mixed together heated and added to a heated porous support or aheated porous support is added to the solutions such that the totalvolume of the bulky ligand metallocene-type catalyst compound solutionand the activator solution or the bulky ligand metallocene-type catalystcompound and activator solution is less than four times the pore volumeof the porous support, more preferably less than three times, even morepreferably less than two times; preferred ranges being from 1.1 times to3.5 times range and most preferably in the 1.2 to 3 times range.

[0112] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density of Fluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0113] Polymerization Process

[0114] The activators of the invention, catalyst systems and supportedcatalyst systems utilizing the activators described above are suitablefor use in any prepolymerization and/or polymerization process over awide range of temperatures and pressures. The temperatures may be in therange of from −60° C. to about 280° C., preferably from 50° C. to about200° C., and the pressures employed may be in the range from 1atmosphere to about 500 atmospheres or higher.

[0115] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Particularlypreferred is a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene.

[0116] In one embodiment, the process of the invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the polymerizationof two or more olefin monomers of ethylene, propylene, butene-1,pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[0117] Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbomene, norbomadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

[0118] In another embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

[0119] In another embodiment of the process of the invention, ethyleneor propylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

[0120] In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms.

[0121] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0122] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0123] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0124] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

[0125] In another embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0126] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C. to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0127] In another embodiment, the polymerization technique of theinvention is referred to as a particle form polymerization, or a slurryprocess where the temperature is kept below the temperature at which thepolymer goes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. Other slurry processes include thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

[0128] In another embodiment the reactor used in the slurry process ofthe invention is capable of and the process of the invention isproducing greater than 2000 lbs of polymer per hour (907 Kg/hr), morepreferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferablygreater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment theslurry reactor used in the process of the invention is producing greaterthan 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greaterthan 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500Kg/hr).

[0129] Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525, whichare fully incorporated herein by reference.

[0130] In one embodiment of the process of the invention is the process,preferably a slurry or gas phase process is operated in the presence ofthe catalyst system of the invention and in the absence of oressentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This process isdescribed in PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352 and5,763,543, which are herein fully incorporated by reference.

[0131] In another embodiment, the method of the invention provides forinjecting a the catalyst system of the invention into a reactor,particularly a gas phase reactor. In one embodiment the catalyst systemis used in the unsupported form, preferably in a liquid form such asdescribed in U.S. Pat. Nos. 5,317,036 and 5,693,727 and Europeanpublication EP-A-0 593 083, all of which are herein incorporated byreference. The polymerization catalyst in liquid form can be fed with anactivator, and/or a support, and/or a supported activator together orseparately to a reactor. The injection methods described in PCTpublication WO 97/46599, which is fully incorporated herein byreference, may be utilized. Where an unsupported catalyst system is usedthe mole ratio of the metal of the Lewis acid activator component to themetal of the phenoxide transition metal catalyst compound is in therange of between 0.3:1 to 10,000:1, preferably 100:1 to 5000: 1, andmost preferably 500:1 to 2000:1.

[0132] Polymer Products

[0133] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers.

[0134] The polymers, typically ethylene based polymers, have a densityin the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range offrom 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/ccto 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

[0135] The polymers produced by the process of the invention typicallyhave a molecular weight distribution, a weight average molecular weightto number average molecular weight (M_(w)/M_(n)) of greater than 1.5 toabout 15, particularly greater than 2 to about 10, more preferablygreater than about 2.2 to less than about 8, and most preferably from2.5 to 8.

[0136] Also, the polymers of the invention typically have a narrowcomposition distribution as measured by Composition Distribution BreadthIndex (CDBI). Further details of determining the CDBI of a copolymer areknown to those skilled in the art. See, for example, PCT PatentApplication WO 93/03093, published Feb. 18, 1993, which is fullyincorporated herein by reference.

[0137] The polymers of the invention in one embodiment have CDBI'sgenerally in the range of greater than 50% to 100%, preferably 99%,preferably in the range of 55% to 85%, and more preferably 60% to 80%,even more preferably greater than 60%, still even more preferablygreater than 65%.

[0138] In another embodiment, polymers produced using a catalyst systemof the invention have a CDBI less than 50%, more preferably less than40%, and most preferably less than 30%.

[0139] The polymers of the present invention in one embodiment have amelt index (MI) or (I₂) as measured by ASTM-D-1238-E in the range fromno measurable flow to 1000 dg/min, more preferably from about 0.01dg/min to about 100 dg/min, even more preferably from about 0.1 dg/minto about 50 dg/min, and most preferably from about 0.1 dg/min to about10 dg/min.

[0140] The polymers of the invention in an embodiment have a melt indexratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to lessthan 25, more preferably from about 15 to less than 25.

[0141] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

[0142] In yet another embodiment, propylene based polymers are producedin the process of the invention. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117, all of which are herein incorporated byreference.

[0143] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes, elastomers, plastomers, high pressurelow density polyethylene, high density polyethylenes, polypropylenes andthe like.

[0144] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, pipe,geomembranes, and pond liners. Molded articles include single andmulti-layered constructions in the form of bottles, tanks, large hollowarticles, rigid food containers and toys, etc.

EXAMPLES

[0145] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

[0146] Tris-pentafluorophenylaluminum Al(C₆F₅)₃ was synthesized via thereaction of one equivalent of tris-pentafluorophenylborane B(C₆F₅)₃(from Boulder Scientific, Mead, Colo.) with one equivalent oftrimethylaluminum as described by Paolo Biagini et al. in U.S. Pat. No.5,602,269. [CH₃Al(C₆F₅)₂]₂ was synthesized by dissolving B(C₆F₅)₃ intoluene previously dried over sodium/potassium alloy and adding dropwisetwo equivalents of trimethylaluminum. The solvent was removed undervacuum, pentane was added, and the solution cooled to −30° C. Anhydroustoluene and pentane were purchased from Aldrich, Milwaukee, Wis.Triphenylmethanol (C₆H₅)₃COH was also purchased from Aldrich and used asreceived. X-Ray Diffraction studies were performed by CrystalyticsCompany.

Example 1 (C₆H₅)₃C⁺[HO(Al(C₆F₅)₃)₂] Synthesis

[0147] Al(C₆F₅)₃ (5.15 grams) and 2.33 grams of (C₆H₅)₃COH were combinedin toluene at room temperature. A dark brick red slurry formedimmediately upon mixing the two reagents. A red oil separated from themixture. The toluene was decanted from the oil and several 30 mlportions of pentane was added to the red oil until the oil crystallizedinto a yellow solid. Crystals of the complex were grown out ofdichloromethane. An X-ray diffraction study of a crystal of this complexrevealed a dimer complex in the solid state with the following formula:(C₆H₅)₃C⁺[HO(Al(C₆F₅)₃)₂]⁻. (FIG. 1). ¹⁹F NMR (CD₂Cl₂); ref. toCF₃C₆H₅δ=−62.5:δ(d, −121.93), (t, −155.65),(m, −163.49). ¹H NMR(CD₂Cl₂); δ(s, 5.18), (d, 7.67), (t, 7.89), (t, 8.29). (FIG. 2).

Example 2 [Me₂AlOC(C₆H₅)₃]₂ Synthesis

[0148] 10.0 grams of trimethylaluminum was combined with one equivalentof (C₆H₅)₃COH in toluene. A white precipitate forms which was filtered,washed with pentane and dried under vacuum. ¹H NMR (C₆D₆); d(s, −0.735),(m, 7.18), (d, 7.67).

Example 3 (C₆H₅)₃C⁺[Me_(x)(C₆F₅)_(y)OAln]⁻ Synthesis

[0149] Al(C₆F₅)₃(toluene) (9.08 grams) and 5.0 grams of[Me₂AlOC(C₆H₅)₃]₂ were combined in benzene at room temperature. A darkbrick red slurry formed immediately upon mixing the two reagents. A redoil separated from the mixture. The toluene was decanted from the oiland several 30 ml portions of pentane was added to the red oil until theoil crystallized into a orange solid. (C₆H₅)₃CCH₃ (1.75 grams) wasisolated from the pentane fractions. ¹H NMR (CD₂Cl₂); δ(0-−1.5 broadlump —Al—CH₃), (d, 7.66), (t, 7.89), (t, 8.29). ¹⁹F NMR (C₆D₆;δ(−120-−125 broad with spikes (doublets)), (−149-−159 broad with spikes(triplets)), , (−160-−166 broad with spikes (multiplets)). ElementalAnalysis; Carbon, 47.63%; Hydrogen, 1.46%; Fluorine, 36.32%.

[0150] The polymerization reactions of Examples 4 to 7 were conducted ina stainless steel, 1-liter Zipperclave autoclave reactor. The reactorwas equipped with water jacket for heating and cooling. Injections weretypically done through a septum inlet or were injected via a highpressure nitrogen injection. Before polymerization the reactor waspurged with nitrogen for several hours at 100° C. Upon injection ofcatalyst, ethylene was fed continuously on demand keeping the reactorpressure constant while maintaining the reaction temperature at 60° C.The reaction was stopped by cooling and venting the pressure andexposing the contents of the reactor to air. The liquid components wereevaporated and the poly(ethylene-co-hexene-1) was dried in a vacuumoven. Weight average molecular weight (M_(w)), number average molecularweight (M_(n)) and their ratio M_(w)/M_(n) were obtained by GPC gelpermeation chromatography.

Example 4 (n-BuCP)₂Zr(CH₃)₂) (20 mg) and (C₆H₅)₃C⁺[HO(Al(C₆F₅)₃)₂]⁻

[0151] (79 mg) were combined in 10 mls of toluene. 2 mls of the catalystprecursor solution was injected into a 1L stainless steel reactorpreheated to 60° C. containing 45 mls of hexene, 75 psi (517 kPa) ofethylene, and 400 mls of toluene. After 15 minutes the polymerizationreaction was stopped. Polymer was not obtained.

Example 5 (n-BuCP)₂Zr(CH₃)₂) (20 mg) and (C₆H₅)₃C⁺[HO(Al(C₆F₅)₃)₂]⁻/(5□1Me₃Al)

[0152] (79 mg) were combined in 10 mls of toluene. 2 mls of the catalystprecursor solution (light blue) was injected into a 1L stainless steelreactor preheated to 60° C. containing 45 mls of hexene, 75 psi (517kPa) of ethylene, and 400 mls of toluene. After 15 minutes thepolymerization reaction was stopped and 6.10 grams of polymer wereisolated. Mw=260,000, Mn=135000, Mw/Mn=1.92; Hexene wt %=2.4.

Example 6 (n-BUCP)₂Zr(CH₃)₂) (20 mg) and (C₆H₅)₃C⁺[Me_(x)(C₆F₅)_(y)OAl]⁻

[0153] (79 mg) were combined in 10 mls of toluene. 2 mls of the catalystprecursor solution was injected into a 1L stainless steel reactorpreheated to 60° C. containing 45 mls of hexene, 75 psi (517 kPa) ofethylene, and 400 mls of toluene. After 30 minutes the polymerizationreaction was stopped and 27.5 grams of polymer were isolated. Mw=592000,Mn=288000, Mw/Mn=2.05; Hexene wt %.

Example 7 Ethylene-Hexene Copolymerizations

[0154] {[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}Hf(CH₂Ph)₂ (22 mg) and(C₆H₅)₃C⁺[Me_(x)(C₅F₅)_(y)O_(n)Al_(m)]⁻ (46 mg) were combined in 10 mlsof toluene. 2 mls of the catalyst solution was injected into a 1Lstainless steel reactor preheated to 60° C. containing 45 mls of hexene,75 psi (517 kPa) of ethylene, and 400 mls of toluene. After 30 minutesthe polymerization reaction was stopped and 11.0 grams of polymer wereisolated. Run 2: 2×2 mls of catalyst solution were injected into thereactor and 26.8 grams of polymer were isolated. Mw=116,000, Mn=63,900,Mw/Mn=1.81; Hexene wt %=38.5. Run 2: 2×2 mls of catalyst solution wereinjected into the reactor and 26.8 grams of polymer were isolated.Mw=208,000, Mn=62,600, Mw/Mn=1.96; Hexene wt %=37.1.

Example 8 Catalyst A Synthesis

[0155] 4.0 grams of silica (Davison 948, calcined at 600° C.) wasslurried in toluene. 0.758 grams of Me₂AlOC(C₆H₅)₃ and 0.92 grams ofAl(C₆F₅)₃(toluene) were added to the silica slurry. The resulting darkred slurry was stirred for one hour and left to sit overnight. Thefollowing day the slurry was filtered, washed with toluene and driedunder vacuum forming a free flowing orange solid. (5.1 grams). 2.5 gramsof this supported activator was combined in toluene with 0.1 grams of(n-BuCP)₂Zr(CH₃)₂. The slurry was stirred for one hour, filtered, rinsedwith toluene, and dried under vaccuum.

Example 9 Catalyst B Synthesis

[0156] Tris-pentafluorophenylaluminum was reacted with silica (Davison948, 600° C.) to liberate pentafluorobenzene in a toluene slurry. Afterapproximately 24 hours the slurry was filtered and washed with three 50ml portions of toluene. The resulting silica was reacted with 2.34 gramsof triphenylmethanol. An immediate dark brick red color forms in thesilica. After one hour the silica was rinsed with toluene, and combinedwith 5.17 grams of Al(C₆F₅)₃(toluene). The slurry was stirred for onehour, filtered, rinsed with toluene (3 50 ml portions) and driedovernight under vacuum. A free-flowing yellow solid resulted. 2.0 gramsof this supported activator was combined in toluene with 0.1 grams of(n-BuCP)₂Zr(CH₃)₂. The slurry was stirred for one hour, filtered, rinsedwith toluene, and dried under vaccuum.

Example 10 (C₆H₅)₃COC₆F₄C₆F₅ Synthesis

[0157] 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol (15.3 grams) wascombined with one equivalent of potassium hydride (1.8 grams) in atetrahydrofuran solution. The evolution of hydrogen gas resulted,yielding a colorless solution. Triphenylmethyl chloride (12.8 grams) wasadded to the solution. A white precipitate formed after stirring severalhours. the tetrahydrofuran was removed and replaced withdichloromethane. The slurry was filtered, and the potassium chloridesalt was washed with several mls of dichloromethane. The solution wasdried under vacuum yielding a white solid (25 grams). ¹⁹F NMR (C₆D₆);ref. to CF₃C₆H₅δ=−62.5:δ(m, −134.8), (m, −137.5), (t, −142.2), (t,−146.9), (t, −157.0).

Example 11 Catalyst C Synthesis

[0158] (C₆H₅)₃COC₆F₄C₆F₅ (1.7 grams) was slurried in anhydrous decanewith 2.0 grams of triethylaluminum treated silica (1.2 mmoles oftriethylaluminum combined in a pentane slurry of Davison 948(calcined at600° C.), filtered and dried). The slurry was heated overnight at 100°C. The resulting slurry was washed with several 30 ml portions oftoluene. (The filtrate contained 0.5 grams of triphenylmethane.) Thesilica was then tranferred to a 100 ml flask slurried in toluenecombined with 0.048 grams of (1,3MeBuCp)₂Zr(CH₃)₂ and stirred at roomtemp. for one hour. The silica was filtered, rinsed with toluene, anddried under vacuum.

[0159] The polymerization reactions of Examples 12 to 14 were conductedin a stainless steel, 1-liter Zipperclave autoclave reactor. The reactorwas equipped with water jacket for heating and cooling. Injections wereperformed via a high pressure nitrogen injection. (400 mls isobutane, 30mls of hexene, and 15 μls triethylaluminum or 100 μlstriisobutylaluminum) Before polymerizations the reactor was purged withnitrogen for several hours at 100° C. Upon injection of catalystethylene was fed continuously on demand keeping the reactor pressureconstant (130 psig (896 kPa) ethylene) while maintaining the reactiontemperature at 85° C. After the allotted time the reaction was stoppedby cooling and venting the pressure and exposing the contents of thereactor to air. The liquid components were evaporated and thepoly(ethylene-co-hexene-1) resin was dried under a N₂ purge. Weightaverage molecular weight (M_(w)), number average molecular weight(M_(n)) and their ratio M_(w)/M_(n) were obtained by GPC gel permeationchromotagraphy. Hexene wt % incorporation was obtained from ¹H NMR data.

Example 12 Slurry-Phase Ethylene-Hexene Polymerization Using Catalyst A

[0160] The above procedure was performed using 25 mgs of Catalyst A.After 40 minutes the reaction was stopped. Some reactor fouling wasobserved and 36.8 grams of polymer resin (2450 g pol. /g cat. h) wasobtained. Mw=112000, Mn=50000, Mw/Mn=2.24; Hexene wt %=5.7.

Example 13 Slurry-Phase Ethylene-Hexene Polymerization Using Catalyst B

[0161] The polymerization was run according to the procedure outlinedabove using catalyst B. No reactor fouling was observed and the polymerresin yield was Run 1: 53.4 grams (3560 g pol./g cat. h). Mw=92800,Mn=43600, Mw/Mn=2.13; Hexene wt %=6.4. Run 2: 71.6 grams (4770 g pol./gcat. h). Mw=88300, Mn=40500, Mw/Mn=2.05; Hexene wt %=2.18.

Example 14 Slurry-Phase Ethylene-Hexene Polymerizations using Catalyst C

[0162] The polymerization was run according to the procedure outlinedabove using catalyst C, The polymer resin yield was Run 1: 50.5 grams(3060 g pol./g cat. h: Run 2: 59.5 grams (3606 g pol./g cat. h).Mw=165,000, Mn=72,700, Mw/Mn=2.27; Hexene wt %=5.5. Run 2: 59.5 grams(3606 g pol./g cat.h). Mw=165,000, Mn=76,600, Mw/Mn=2.16; Hexene wt%=5.4.

[0163] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that theactivator compositions of the invention may be used in combination witheach other and with known actuator compositions to activatepolymerization catalyst compound(s). Furthermore, it is contemplatedthat any one of the embodiment(s) of this invention may be combined withany other embodiment(s) of the invention. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

I claim:
 1. A process for polymerizing olefin(s) in the presence of acatalyst system comprising: a) a polymerization catalyst; and b) anactivator complex comprising a perfluorophenyl aluminum compound and atrityl source, where the perfluorophenyl aluminum is represented byAl(C₆F₅)_(m)R_(n) where m+n=3; each R is independently selected from thegroup consisting of monoanionic ligand, hydrogen, a hydroxyl group, analkyl group, and combinations thereof.
 2. The process of claim 1 wherethe catalyst system further comprises a support.
 3. The process of claim1 where R is a halogenated C₆ aromatic or higher carbon numberpolycyclic aromatic hydrocarbon or aromatic ring assembly in which twoor more rings (or fused ring systems) are joined directly to one anotheror together.
 4. The process of claim 1 where R is represented by theformula [M^(k+)Q_(n)]^(d−) where k is an integer from 1 to 3; n is aninteger from 2 to 6; n−k=d; M is an element selected from Group 13 ofthe Periodic Table of the Elements, and each Q is independently selectedfrom the group consisting of a hydride, bridged or unbridgeddialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl,halosubstituted-hydrocarbyl radicals having up to 20 carbon atoms, andcombinations thereof.
 5. The process of claim 1 where theperfluorophenyl aluminum is represented by(AlO)_(x)(Al)_(y)(C₆F₅)_(z)(R)d where x cannot be 0 and z+d is≦1+3(x+y); R may be OH, R or OR, and is independently selected from thegroup consisting of a monoanionic ligand, hydrogen, a hydroxyl group,and an alkyl group, and where R may bridge to the Al.
 6. The process ofclaim 4 where R is a halogenated C₆ aromatic or higher carbon numberpolycyclic aromatic hydrocarbon or aromatic ring assembly in which twoor more rings (or fused ring systems) are joined directly to one anotheror together.
 7. The process of claim 5 where R is represented by theformula [M^(k+)Q_(n)]^(d−) where k is an integer from 1 to 3; n is aninteger from 2 to 6; n−k=d; M is an element selected from Group 13 ofthe Periodic Table of the Elements, and each Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals having up to 20carbon atoms.
 8. The process of claim 1 where the trityl source isrepresented by the formula (C₆H₅)₃COL where L is selected from the groupconsisting of a metal moiety, a metalloid moiety, a monoanionic ligand,hydrogen, a hydroxyl group, and an alkyl group.
 9. The process of claim8 where L is a halogenated C₆ aromatic or higher carbon numberpolycyclic aromatic hydrocarbon or aromatic ring assembly in which twoor more rings (or fused ring systems) are joined directly to one anotheror together.
 10. The process of claim 8 where L is represented by theformula [M^(k+)Q_(n)]^(d−) where k is an integer from 1 to 3; n is aninteger from 2 to 6; n−k=d; M is an element selected from Group 13 ofthe Periodic Table of the Elements, and each Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals having up to 20carbon atoms.
 11. The process of claim 8 where the metal may berepresented by the formula AlR₂, TiR₃, Ti(Benzyl)₃ or ZrR₃ where each Ris independently a monoanionic ligand, hydrogen, a hydroxyl group, or analkyl group.
 12. The process of claim 1 where the polymerizationcatalyst is selected from the group consisting of a bulky ligandmetallocene catalyst compound, a metal containing Group 15polymerization catalyst compound, a phenoxide transition metal catalystcompound, and combinations thereof.
 13. A process for polymerizingolefin(s) in the presence of a catalyst system comprising: a) apolymerization catalyst; and b) an activator represented by the formula:[Al(C₆F₅)_(m)R_(n)]x[(C₆H₅)₃COL]y   (III) where x and y may or may notbe integers and represent the ratio in which [Al(C₆F₅)_(m)R_(n)] and[(C₆H₅)₃COL] are combined; m+n=3; each R may independently be amonoanionic ligand, hydrogen, a hydroxyl group, or an alkyl group; andeach L may independently be a metal moiety, a metalloid moiety, amonoanionic ligand, hydrogen, a hydroxyl group, or an alkyl group. 14.The process of claim 13 where any L or R may be a halogenated C₆aromatic or higher carbon number polycyclic aromatic hydrocarbon oraromatic ring assembly in which two or more rings (or fused ringsystems) are joined directly to one another or together.
 15. The processof claim 13 where any L or R may be represented by the formula[M^(k+)Q_(n)]^(d−) where k is an integer from 1 to 3; n is an integerfrom 2 to 6; n−k=d; M is an element selected from Group 13 of thePeriodic Table of the Elements, and each Q is independently a hydride,bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, and halosubstituted-hydrocarbyl radicals having up to 20carbon atoms.
 16. The process of claim 13 where the polymerizationcatalyst is selected from the group consisting of a bulky ligandmetallocene catalyst compound, a metal containing Group 15polymerization catalyst compound, a phenoxide transition metal catalystcompound, and combinations thereof.